e-ISSN: 2073-4344

Project code: CTQ2016-75016-R

Keywords: Solventless reaction Polycarbonates Metalloporphyrin Fluorinated catalyst Epoxide Copolymerisation Compressed co2 Compressed co 2 Chromium

Record's date: 2023-02-22

Papper version: info:eu-repo/semantics/publishedVersion

Licence document URL: http://repositori.urv.cat/ca/proteccio-de-dades/

Papper original source: Catalysts. 7 (7):

APA: Carrilho, Rui M. B. Dias, Lucas D. Rivas, Raquel Pereira, Mariette M. Claver, Carmen Masdeu-Bulto, Anna M. (2017). Solventless Coupling of Epoxides and CO2 in Compressed Medium Catalysed by Fluorinated Metalloporphyrins. Catalysts, 7(7), -. DOI: 10.3390/catal7070210

Acronym: ECO2VALCAT

Publication Type: Journal Publications

Author, as appears in the article.: Carrilho, Rui M. B. Dias, Lucas D. Rivas, Raquel Pereira, Mariette M. Claver, Carmen Masdeu-Bulto, Anna M.

Department: Química Física i Inorgànica

URV's Author/s: Claver Cabrero, Maria del Carmen Orosia / Masdeu Bultó, Anna Maria / Rivas Del Valle, Raquel

Abstract: Metal complexes of meso-arylporphyrins (Cr(III), Fe(III), and Zn(II)) were evaluated in the coupling reaction of cyclohexene oxide (CHO) with CO2 in compressed medium, where the Cr complexes were demonstrated to be the most active systems, leading predominantly to copolymerisation products. It is noteworthy that no addition of solvent was required. To improve the catalytic activity, and to simultaneously increase the solubility in compressed CO2, a new fluorinated catalyst, tetrakis(4-trifluoromethylphenyl)porphyrinatochromium(III) chloride (CrCl-pCF3TPP), was applied to this reaction. The alternating copolymerisation of CHO with CO2, using the Cr(III) fluorinated porphyrin catalyst, required the use of a co-catalyst, bis(triphenylphosphine)iminium chloride (PPNCl), with the best yields of copolymers being obtained at 80 ◦C, and CO2 pressures in the range of 50-110 bar, over a period of 24 h, with a low catalyst/substrate molar ratio (0.07%). The polycarbonate's structure was analysed by 1H NMR, 13C NMR, and MALDI-TOF spectroscopy, which demonstrated high carbonate incorporations (98-99%). Gel permeation chromatography revealed number-average molecular weights (Mn) in the range of 4800-12,800 and narrow molecular weight distributions (Mw/Mn ≤ 1.63).

Thematic Areas: Química Physical and theoretical chemistry Farmacia Environmental science (all) Engenharias ii Ciências biológicas ii Chemistry, physical Catalysis Astronomia / física

licence for use: https://creativecommons.org/licenses/by/3.0/es/

ISSN: 20734344

Author's mail: carmen.claver@urv.cat annamaria.masdeu@urv.cat raquel.rivas@urv.cat raquel.rivas@urv.cat

Author identifier: 0000-0002-2518-7401 0000-0001-7938-3902 0000-0002-2007-7481 0000-0002-2007-7481

Journal volume: 7

Link to the original source: https://www.mdpi.com/2073-4344/7/7/210

Funding program: PROGRAMA ESTATAL DE INVESTIGACIÓN, DESARROLLO E INNOVACIÓN ORIENTADA A LOS RETOS DE LA SOCIEDAD

Article's DOI: 10.3390/catal7070210

Entity: Universitat Rovira i Virgili

Journal publication year: 2017

Funding program action: VALORIZACION EFICIENTE DE CO2 A COMBUSTIBLES Y COMPUESTOS DE ALTO VALOR AÑADIDO MEDIANTE CATALISIS HOMOGENEA Y NANO-CATALISIS